Water insoluble styryl dyestuffs having hetero-aryl methylene substituent

ABSTRACT

The invention relates to water-insoluble styryl dyestuffs of the formula ##STR1## wherein B is a bridge member, R is hydrogen, alkyl, aryl or the remaining members of a partially saturated ring fused to the ring &#34;a&#34;, Z is preferably CN and n denotes the numbers 3 to 5. 
     The dyestuffs are outstandingly suitable for the dyeing of hydrophobic fibre materials in yellow shades. The dyeings are distinguished by excellent fastness to light.

This is a division of application, Ser. No. 616,262, filed Sept. 24,1975 now U.S. Pat. No. 4,016,191, issued Apr. 5, 1977.

The present invention relates to dyestuffs which are practicallyinsoluble in water, of the formula ##STR2## wherein B represents abridge member,

R represents hydrogen, alkyl, aryl or the remaining members of apartially saturated 5-membered or 6-membered ring fused to the ring "a",

Z represents the groupings CN, SO₂ Y, COY, CO₂ Y or CONW₁ W₂,

wherein

Y denotes alkyl, cycloalkyl, aralkyl or aryl and

W₁ and W₂ conjointly with the N atom can form the remaining members of a5-membered to 7-membered saturated heterocyclic ring, and

N denotes the numbers 3 to 5

And wherein

The alkyl, cycloalkyl, aralkyl and aryl radicals mentioned, and therings "a" and "b" can contain further non-ionic substituents and inaddition the rings "a" and "b" can contain further fused-on rings,

As well as to their manufacture and use for dyeing and printingsynthetic fibre materials and for bulk dyeing of thermoplastics.

Suitable "non-ionic substituents" are groups which are customary instyryl dyestuff chemistry and do not confer solubility in water in theneutral to acid range, or groups such as are mentioned below inconnection with the preferred dyestuffs.

Suitable "bridge members" in the sense of the invention arenon-chromophoric members, preferably C₂ - to C₅ -alkylene chains whichare optionally interrupted by an oxygen atom or sulphur atom and whichcan also be branched and/or be substituted by a C₁ - to C₄ -alkoxy or-alkenyloxy group or a benzyloxy or phenoxy group.

Suitable alkyl radicals are those with 1 to 4 C atoms, which can besubstituted by halogen, CN, COOH or C₁ - to C₄ -alkoxy. Methyl and ethylare very particularly preferred.

Suitable aryl radicals are phenyl and naphthyl radicals which can besubstituted, preferably monosubstituted to trisubstituted, by halogen,C₁ to C₄ -alkyl, C₁ to C₄ -alkoxy, C₁ to C₄ -alkylmercapto, benzyl,cyclopentyl or cyclohexyl. Optionally substituted phenyl radicals areparticularly preferred.

The cycloalkyl radicals mentioned are above all cyclopentyl andcyclohexyl radicals which can in turn be monosubstituted, disubstitutedor trisubstituted by chlorine, methyl and others.

Suitable aralkyl radicals are, above all, benzyl, phenethyl andphenylpropyl.

Suitable heterocyclic rings which W₁ and W₂ can form are piperidine,pyrrolidine, N-methyl-piperazine, morpholine or thiomorpholine.

Preferably, W₁ and W₂ do not simultaneously represent aryl and/orcycloalkyl.

Particularly suitable substituents in the ring "a" are halogen, C₁ - toC₃ -alkyl, C₁ to C₃ -alkoxy, C₂ to C₅ -alkanoyloxy, C₂ - to C₅-alkanoylamino, benzoyloxy, benzoylamino or phenoxy. Preferably, 1 to 3of these substituents are present. Preferentially suitable substituentsin the ring "b" are C₁ to C₄ -alkyl, C₁ -C₄ -alkoxy, CN or COOH.

In the preceding text "halogen" is to be understood as fluorine and,preferably, chlorine or bromine.

A group of preferred dyestuffs according to the invention corresponds tothe formula ##STR3## wherein X represents C₁ - to C₄ -alkyl, C₁ - to C₄-alkoxy, CN or hydrogen,

n represents 4-5,

B' represents --C₂ H₄ --, --C₃ H₆ --, --C₄ H₈ --, --CH(CH₃)CH₂ --,--CH(C₆ H₅)CH₂ --, --CH(CH₂ OCH₃)CH₂ --, --CH(CH₂ OC₂ H₅)CH₂ --,--CH(CH₂ OCH₂ CH═CH₂)CH₂ --, --CH(CH₂ OC₆ H₅)CH₂ -- or --CH(CH₂ OCH₂ C₆H₅)CH₂ --,

R' represents CH₃, C₂ H₅, C₃ H₇, CH₂ C₆ H₅, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂H₄ CN, C₂ H₄ C₆ H₅, CH₂ CH(C₆ H₅)CH₃ or (CH₂)₃ C₆ H₅,

Y₁ represents hydrogen, C₁ - to C₄ -alkyl, C₁ - to C₄ -alkoxy, CF₃, C₂ -to C₄ -alkanoylamino, phenoxy, F, Cl or Br,

Y₂ represents hydrogen, C₁ - to C₄ -alkyl, C₁ - to C₄ -alkoxy, chlorineor bromine and

Z' represents CN or COOQ',

wherein

Q' denotes C₁ - to C₄ -alkyl, phenyl-C₁ - to -C₃ -alkyl or cyclohexyl.

A further group of preferred dyestuffs in the sense of the invention arethose of the formula II wherein

R' and Y₂ conjointly form the missing members of the partiallysubstituted, optionally methyl-, ethyl- or chlorine-substituted,heterocyclic structure of an indoline, 1,2,3,4-tetrahydroquinoline,2,3-dihydrobenzoxazine-(1,4) or 2,3,4,5-tetrahydrobenzazepine ringsystem.

Particularly preferred dyestuffs according to the invention are those ofthe formula ##STR4## wherein X and n have the abovementioned meaningsand

R" denotes a methyl, ethyl, propyl, benzyl, phenethyl or phenpropylgroup and

Y³ denotes hydrogen or a methyl group.

Particularly valuable dyestuffs, within the scope of the invention, havethe formula ##STR5## wherein X' represents hydrogen, methyl, ethyl or acyano group and

n' represents 4 or 5.

Most valuable dyestuffs are those of the abovementioned formulae

wherein

n and n'=5.

The new dyestuffs are prepared in a manner which is in itself known, byreacting aldehydes of the formula ##STR6## or their functionalderivatives, for example those of the formula ##STR7## wherein n, B, R,a and b have the meanings indicated under formula I and

A represents ═N--R¹ (aldimines) or ##STR8## (imonium salts) wherein

R¹ preferably denotes a phenyl, sulphophenyl or carboxyphenyl radical,

R² and R³ represent C₁ - to C₄ -alkyl and

R³ also represents phenyl and

An.sup.⊖ represents an acid anion, preferably Cl⁻ or Br⁻, withmethylene-active compounds of the formula ##STR9## wherein Z can havethe meanings indicated under formula I.

The reactions are carried out at temperatures between 20° and 160° C.,preferably in the temperature range of 50°-120° C., in the melt or, inmost cases, in a solvent which is inert under the reaction conditions.Examples of suitable solvents which may be mentioned are lower aliphaticalcohols with 1 to 4 carbon atoms, especially methanol, ethanol, thepropanols and butanols, and also benzene, toluene, xylene,chlorobenzene, dichlorobenzenes, chloroform, dimethylformamide,dimethylsulphoxide and acetonitrile. To accelerate the reaction, thebasic catalysts customary for the Knoevenagel reaction can be added,such as, for example, ammonia, diethylamine, triethylamine, piperidine,morpholine, N-ethylpiperidine, N-methylmorpholine, basic ion exchangeresins, alkali metal hydroxides, alkali metal alcoholates, alkali metalcarbonates, alkali metal acetates, and acetates of ammonia and oforganic bases, such as, for example, ammonium acetate or piperidineacetate. However, the reaction can also be carried out readily in thepresence of acetic acid and even in glacial acetic acid as the solvent.

It is also possible, with advantage, to dispense with the customaryisolation of the aldehydes V, which in most cases entails considerablelosses, and to use these aldehydes directly, after decomposition ofexces of Vilsmeier reagent by means of lower aliphatic alcohols andadjusting the pH value to about 6.5-8.5, for condensation with themethylene-active components VI. For this purpose, the presence of anemulsifying additive, for example of oxethylation products of higheralcohols or substituted phenols, can be useful, particularly if aqueousalkali or aqueous ammonia are used to adjust the pH.

Examples of suitable methylene-active compounds VI are malonic aciddinitrile, cyanoacetic acid methyl ester, cyanoacetic acid ethyl ester,cyanoacetic acid propyl ester, cyanoacetic acid butyl ester, cyanoaceticacid cyclohexyl ester, cyanoacetic acid γ-methoxypropyl ester,cyanoacetic acid cyanoethyl ester, cyanoacetic acid β-chloroethyl ester,cyanoacetic acid β-acetoxyethyl ester, cyanoacetic acid benzyl ester,cyanoacetic acid 4-chlorobenzyl ester, cyanoacetic acid3,4-dichlorobenzyl ester, cyanoacetic acid 2,4,6-trichlorobenzyl ester,cyanoacetic acid β-phenoxyethyl ester, cyanoacetic acidβ-(4-chlorophenoxy)-ethyl ester, cyanoacetic acidβ-(4-methylphenoxy)-ethyl ester, cyanoacetic acidβ-(4-tert.-butylphenoxy)-ethyl ester, cyanoacetic acidβ-(4-cyclohexylphenoxy)-ethyl ester, cyanoacetic acid γ-phenoxypropylester, cyanoacetic acid β-phenylethyl ester, cyanoacetic acidγ-phenylpropyl ester, cyanoacetic acid γ-phenylallyl ester, cyanoaceticacid α-naphthylmethyl ester, cyanoacetamide, cyanoacetic acidN-methylamide, cyanoacetic acid N,N-dimethylamide, cyanoacetic acidα-cyanoethylamide, cyanoacetic acid N-n-butylamide, cyanoacetic acidcyclohexylamide, cyanoacetic acid diethylamide, cyanoacetic acidpyrrolidide, cyanoacetic acid piperidide, cyanoacetic acid anilide,cyanoacetic acid 3-chloroanilide, cyanoacetic acid 2-ethoxyanilide,cyanoacetic acid 4-t-butylanilide, cyanoacetic acid 4-cyclohexylanilide,cyanoacetic acid α-naphthylamide, methylsulphonylacetonitrile,n-butylsulphonylacetonitrile, phenylsulphonylacetonitrile and4-t-butylphenylsulphonylacetonitrile.

To prepare suitable aldehydes V or their functional derivatives V a itis possible to use aromatic bases of the formula ##STR10## wherein n, B,R, a and b have the meanings indicated for formula I.

These bases are reacted, in a manner which is in itself known, withso-called Vilsmeier reagents, that is to say mixtures of N-formylcompounds ##STR11## and inorganic acid halides, preferably phosphorusoxychloride, thionyl chloride or phosgene, or are formylated by themethod of Duff (Journal of the Chemical Society [London] 1952, pages1,159-1,164), advantageously in accordance with the variant of GermanPatent Specification No. 1,206,879, Suitable aldimines V a are obtained,for example, in accordance with the instructions in U.S. Pat. No.2,583,551 (Example 17).

Suitable methods for the preparation of the bases VII are those knownfrom the literature for the preparation of N-alkoxyalkyl-anilines andN-aryloxyalkyl-anilines, above all the reaction ofN-halogenoalkyl-anilines, N-halogenoalkylindolines,N-halogenoalkyl-tetrahydroquinolines and the like with thiophenolatesVIII ##STR12## in the melt, or in solvents which are inert under thereaction conditions (aliphatic C₁ - to C₅ -alcohols, benzene, toluene,chlorobenzene, ethylene glycol monoethyl ether or ethylene glycolmonomethyl ether, dimethylformamide, N-methylpyrrolidone and others) attemperatures of up to about 140° C., preferably at 50°-100° C.

The preparation of suitable aldehydes V can also be carried out inanother sequence, by reacting the thiophenolates with already formylatedhalogenoalkyl-anilines, according to ##STR13## wherein Hal denotesbromine or preferably chlorine.

This reaction is also in itself known (compare Example 1 of U.S. Pat.No. 3,635,957).

In the thiophenolates VIII, Me represents 1 equivalent of an alkalimetal ion, alkaline earth metal ion or heavy metal ion. Examples whichmay be mentioned are the ions of lithium, sodium, potassium, magnesium,calcium, lead, copper or silver, preferably those of sodium andpotassium. The thiophenolates can be employed as such, but are suitablyproduced in the reaction medium itself, if appropriate in the presenceof the halogenoalkyl compounds, from the corresponding thiophenols, byadding at least one equivalent of a metal compound. Examples of suitablecompounds for this purpose are the oxides, hydroxides, bicarbonates,carbonates, acetates and the like. The use of equivalent amounts oforganic bases, such as, for example, triethylamine, tripropylamine,tri-(hydroxypropyl)-amine, tributylamine, N-methylpiperidine,N-ethylpiperidine, N-methylmorpholine, dimethylaniline or pyridine, inorder to bind the hydrogen halide, is also possible. The reactions arecarried out in the melt or in organic solvents which are inert under thereaction conditions. They take place slowly even at room temperature butare suitably carried out at elevated temperatures, preferably in therange of 50°-150° C.

Example of suitable solvents are lower alcohols, such as methanol,ethanol, propanols, butanols, or amyl alcohols, and also toluene,xylene, dimethylformamide and N-methylpyrrolidone.

A further method of preparation of the bases VII is to reacthalogenoalkyl-thioethers X with secondary bases XI in a manner which isin itself known, in accordance with the following equation: ##STR14##wherein X, n, B, Hal, R and a have the meanings indicated in thepreceding text.

The reaction takes place in solvents which are inert under the reactionconditions, for example in toluene, xylene, chlorobenzene ordichlorobenzene or in higher alcohols, such as butyl alcohols and amylalcohols, in the presence of customary hydrogen halide acceptors, suchas alkali metal oxides, hydroxides or carbonates or alkaline earth metaloxides, hydroxides or carbonates, or organic bases, such astributylamine or dimethylaniline, at temperatures of about 80°-200° C.,preferably at 120°-160° C. A particularly advantageous embodiment of thereaction utilises the secondary base XI simultaneously as a hydrogenhalide acceptor and solvent by using it in at least twice the equivalentamount and within the temperature range indicated above.

To facilitate the reactions of X with XI, catalytic amounts of iodides,for example sodium iodide, potassium iodide or copper iodide, can beadded (compare German Auslegeschrift (German Printed Application) No.2,010,491, Example 2).

The N-halogenoalkylanilines or halogenoalkyl-thioethers X which canalternatively be used for the preparation of the N-arylmercaptoalkylbases VII are most simply accessible respectively from the correspondingsecondary aniline bases XI and the thiophenols VIII (Me=H) by convertingthese into the hydroxyalkyl compounds by oxalkylation, for example bymeans of ethylene carbonate, ethylene oxide, propylene oxide, methylglycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, phenylglycidyl ether or benzyl glycidyl ether or styrene oxide or by reactionwith halogenoalkanols, for example β-halogenoethanols, halogenopropanolsor halogenobutanols, and obtaining the halogenoalkyl compounds therefromby the action of acid halides, such as phosphorus oxychloride,phosphorus tribromide or thionyl chloride.

One-stage processes for arriving at the halogenoalkyl compoundsmentioned are also known and entail carrying out a one-sided reaction ofthe secondary bases XI or the thiophenols with dihalogenoalkanes ordihalogenoalkenes, for example 1,2-dibromoethane, 1,2-dichloroethane,1,3-dichloropropane, 1,3-chlorobromopropane, 1,4-dibromobutane,1,4-dibromobut-2-ene or 1,2-dibromopropane, in the presence of ahydrogen halide acceptor.

Suitable thiophenols VIII (Me=H) which can be used for the preparationof the bases VII are, for example, 2,4,6-trichlorothiophenol,2,4,5-trichlorothiophenol, 2,3,4-tri-chlorothiophenol,2,3,5,6-tetrachlorothiophenol, 2,3,4,6-tetrachlorothiophenol,2,3,5,6-tetrachloro-4-cyano-thiophenol, methyltetrachlorothiophenols,ethyltetrachlorothiophenols and pentachlorothiophenol.

Suitable secondary bases XI for the preparation of the bases VII are,for example, N-methyl-aniline, N-methyl-m-toluidine,N-methyl-m-chloroaniline, N-methyl-m-anisidine,N-ethyl-2,5-dimethoxy-aniline, N-methyl-m-phenetidine,N-methyl-2,5-diethoxy-aniline, N-ethyl-aniline, N-propyl-aniline,N-n-butyl-aniline, N-benzyl-aniline, N-phenethylaniline,N-β-phenylpropyl-aniline, N-γ-phenylpropyl-aniline, N-ethyl-m-toluidine,N-propyl-m-toluidine, N-n-butyl-m-toluidine, N-benzyl-m-toluidine,N-α-phenylethyl-m-toluidine, N-β-phenylethyl-m-toluidine,N-β-phenylpropyl-m-toluidine, N-γ-phenylpropyl-m-toluidine,N-cyanoethyl-aniline, N-methoxyethyl-m-toluidine,N-ethyl-m-phenoxy-aniline, N-ethyl-m-anisidine, N-ethyl-m-phenetidine,N-ethyl-m-chloroaniline, N-ethyl-o-toluidine, N-ethyl-3-bromoaniline,N-methyl-2-ethylaniline, N-methyl-2-isopropylaniline,N-methyl-2,5-dimethylaniline, N-methyl-2-methoxy-5-methylaniline,N-butyl-3-chloroaniline, N-cyclohexylaniline, N-cyclopentyl-m-toluidine,N-methyl-2,5-dichloroaniline, N-methyl-3-propionylamino-aniline,N-benzyl-m-anisidine, N-propyl-3-trifluoromethyl-aniline,N-ethyl-3-acetamino-aniline, N-cyanoethyl-m-toluidine, 2-methyl-,2-ethyl-, 2-methyl-6-chloro-, 2,5-dimethyl-, 2,3,3-trimethyl-,2,3,3,6-tetramethyl-2,3,3-trimethyl-6-chloro-,2,3,3-trimethyl-6-methoxy- and 2,3,3,7-tetramethyl-2,3-dihydroindole,2-methyl-, 2,7-dimethyl-, 2,2,4-trimethyl-, 2-methyl-7-methoxy-,2-methyl-7-chloro-, 2-methyl-7-bromo-, 2-methyl-7-acetamino-,2-methyl-7-phenyl-, 2,2,4-trimethyl-7-methoxy-,2,2,4-trimethyl-7-bromo-, 2,2,4-trimethyl-7-chloro-,2,2,4-trimethyl-7-trifluoromethyl-, 2-ethyl-7-methyl-,2-n-butyl-7-methyl- and 2-i-propyl-7-methyl-1,2,3,4-tetrahydroquinoline,3,6-dimethyl-, 2,3-dimethyl-, 2,3,6-trimethyl-, 2,2,3-trimethyl-,2,2,3,6-tetramethyl-, 2,2,3-trimethyl-6-methoxy-,2,2,3-trimethyl-6-chloro-, 2,2,3-trimethyl-6-acetamino- and3-ethyl-6-methyl-2,3-dihydrobenzoxazine-(1,4) and3,3-tetramethylene-2-methyl-, 3,3-pentamethylene-2-methyl-,3,3-tetramethylene-2,6-dimethyl-, 3,3-pentamethylene-2,6-dimethyl-,2,3-trimethylene-6-methyl-, 2,3-tetramethylene and2,3-tetramethylene-6-methyl-2,3-dihydroindole.

If the N-hydroxyalkyl derivatives of the abovementioned secondary basesXI are reacted by the Vilsmeier reaction, for example withdimethylformamide and phosphorus oxychloride, the correspondingN-chloroalkyl-aldehydes IX are obtained therefrom in a known manner;these serve for the preparation of the aldehydes V, as explained above.

From the large number of the aldehydes IX which can be prepared and aresuitable for reaction with thiophenols VIII, some may be mentioned byway of examples: N-β-chloroethyl-N-methyl-4-aminobenzaldehyde,N-β-chloroethyl-N-ethyl-4-aminobenzaldehyde,N-β-chloropropyl-N-ethyl-4-aminobenzaldehyde,N-γ-chloropropyl-N-ethyl-4-aminobenzaldehyde,N-β-chloro-β-phenylethyl-N-methyl-m-toluidin-4-aldehyde,N-β-chloroethyl-N-benzyl-m-toluidin-4-aldehyde,N-β-chloroethyl-N-γ-phenylpropyl-m-toluidin-4-aldehyde,N-β-chloro-γ-phenoxypropyl-N-ethyl-m-toluidin-4-aldehyde,N-β-chloroethyl-N-β-phenylpropyl-2-chloro-4-aminobenzaldehyde,N-β-chloroethyl-N-methyl-2,5-dimethoxy-4-aminobenzaldehyde,N-β-bromobutyl-N-methyl-4-aminobenzaldehyde,N-β-chloroethyl-6-formyl-2-methyl-,N-β-chloroethyl-6-formyl-2,7-dimethyl-,N-β-chloroethyl-6-formyl-2,2,4-trimethyl-,N-β-chloroethyl-6-formyl-2-methyl-7-methoxy-,N-β-chloroethyl-6-formyl-2,2,4-trimethyl-7-chloro-,N-β-chloroethyl-6-formyl-2,2,4,7-tetramethyl-,N-β-chloropropyl-6-formyl-2,2,4,7-tetramethyl-,N-γ-chloropropyl-2,2,4-trimethyl-,N-β-chloroethyl-6-formyl-2-ethyl-7-methyl- andN-β-chloroethyl-6-formyl-2,2,4-trimethyl-7-trifluoromethyl-1,2,3,4-tetrahydroquinoline,N-β-chloroethyl-7-formyl-3,6-dimethyl-,N-β-chloroethyl-7-formyl-2,3,6-trimethyl-,N-β-chloroethyl-7-formyl-3-methyl-6-chloro-,N-γ-chloropropyl-7-formyl-2,3,6-trimethyl- andN-β-chloropropyl-7-formyl-3-ethyl-5-methoxy-2,3-dihydroxybenzoxazine-(1,4)and N-β-chlorobutyl-5-formyl-2,3,3-trimethyl-,N-γ-chloropropyl-5-formyl-2,3,3-trimethyl-,N-β-chloropropyl-5-formyl-2,3,3-trimethyl- andN-β-chloroethyl-5-formyl-2,3,3-trimethyl-2,3-dihydro-indole.

Finally, the dyestuffs according to the invention can also be preparedby first condensing the N-halogenoalkylaldehydes IX with themethylene-active compounds VI to give the N-halogenoalkyl-styryldyestuffs XII and then reacting these in a manner which is in itselfknown with thiophenolates VIII, in accordance with the followingequation ##STR15## wherein b, n, Me, Hal, B, R, a and Z have theabovementioned meanings.

The reaction conditions can be selected analogously to Example 1 ofSwiss Patent Specification No. 505,876.

The dyestuffs according to the invention are outstandingly suitable fordyeing and printing hydrophobic fibre materials, especially polyesters,for example those from terephthalic acid and ethylene glycol or1,4-bis-(hydroxymethyl)-cyclohexane, polycarbonates, for example thosefrom α,α-dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, celluloseesters, for example cellulose triacetate, and fibres based on polyvinylchloride.

The dyestuffs are used in accordance with the known dyeing processes,for example in the exhaustion process, as aqueous dispersions in thepresence of customary dispersing agents and, if appropriate, customaryswelling agents (carriers), at temperatures near 100° C., or withoutcarriers at 120°-140° C. (HT process).

Furthermore, they are outstandingly suitable for dyeing in accordancewith the known thermosol process. They do not dye, or only dye slightly,wool and cotton present in the dye bath at the same time, so that theyare very suitable for use in dyeing polyester/wool andpolyester/cellulose fibre mixed fabrics.

Their solubility in numerous organic solvents is excellent, and they canbe used for dyeing lacquers and oils, bulk-dyeing of plastics, such aspolystyrene and polyethylene, and dyeing of fibres in accordance withthe customary spin-dyeing processes.

The dyestuffs according to the invention impart clear yellow colorationsof very good fastness to light and good fastness to washing andsublimation to the hydrophobic materials mentioned.

They can be used for combination dyeing with blue azo and anthraquinonedisperse dyestuffs and in that case given green dyeings on cellulosetriacetate and on polyester, which have good fastness to light and showno "catalytic fading".

The good stability in dye baths, and stability to boiling, of thedyestuffs according to the invention, in neutral to moderately basicliquors or printing pastes (pH stability up to about pH 10) should besingled out particularly; as a result, the dyestuffs are also verysuitable for one-bath dyeing (thermosol-thermofixing process) and forprinting polyester/cotton mixed fabrics in combination with reactivedyestuffs which require the presence of alkali (sodium carbonate orsodium bicarbonate).

In the examples which follow, parts denote parts by weight, unlessexpressly stated otherwise, they bear the same relation to parts byvolume (pts. by vol.) as the gram to the milliliter. The temperaturesquoted are to be understood as degrees centigrade.

EXAMPLE 1

31.1 parts of pentachlorothiophenol and 19.8 parts ofN-ethyl-N-β-chloro-ethyl-m-toluidine are added successively to asolution of 2.53 parts of sodium in 160 parts by volume of ethanol andthe mixture is heated for 6 hours to the reflux temperature. Aftercooling, the product which has crystallised out is filtered off, washedwith a little ethanol and then thoroughly washed with water, and driedin vacuo at 40° C. 43.2 parts ofN-ethyl-N-(β-pentachlorophenylmercaptoethyl)-m-toluidine of meltingpoint 75°-80° C. are obtained. The base is sufficiently pure for thefurther reaction.

For the formylation, 39.9 parts of the crude base are dissolved in 45parts of dimethylformamide, 15.3 parts of phosphorus oxychloride arethen added dropwise whilst stirring and occasionally cooling, in such away that the temperature does not rise significantly above 60° C., andthe mixture is then warmed to 60°-65° C. for 15 hours. The mixture isthen allowed to cool to about 40° C. and is decomposed by dropwiseaddition of 70 parts by volume of methanol over the course of half anhour, whilst maintaining an internal temperature of 40°-50° C. bycooling. Thereafter, the pH value is adjusted to above 8 by adding about30 parts by volume of concentrated aqueous ammonia or an equivalentamount of alkali metal hydroxide solution, whereupon the aldehydeseparates out. It is occasionally first obtained as an oil, butcrystallises throughout on further stirring. It is isolated by filteringoff and washing with a little methanol and then with a copious amount ofwater, and is dried in vacuo. The yield is 38-40 parts ofN-ethyl-N-(β-pentachlorophenylmercaptoethyl)-2-methyl-4-aminobenzaldehydewhich after recrystallisation from toluene forms colourless prisms ofmelting point 137°-138.5° C.

35.2 parts of the aldehyde are dissolved in about 80 parts by volume ofdimethylformamide by warming, 0.25 part by volume of piperidine and 5.3parts of malodinitrile are then added and the mixture is warmed to 70°C. for 2 hours. About 400 parts by volume of methanol are then added,the mixture is stirred for some time longer at 15°-20° C. and thedyestuff which has crystallised out is filtered off. It is thoroughlywashed with methanol and dried in vacuo at 100° C. 35.3 parts ofdyestuff of the formula ##STR16## are obtained.

The dyestuff can be purified by recrystallisation from n-butanol andthen melts at 155°-156° C. However, this is not necessary for its usefor tinctorial applications. The dyestuff dyes polyester fibres andtriacetate rayon in clear, greenish-tinged yellow shades of very goodfastness to light, wet processing and sublimation and shows virtually no"catalytic fading" in green mixtures with blue azo dyestuffs andanthraquinone dyestuffs.

The aldehyde used in this example can also be obtained in accordancewith the following procedure: 2.53 parts of sodium are dissolved in 160parts by volume of ethanol, 31.1 parts of pentachlorothiophenol followedby 22.5 parts of N-ethyl-N-β-chloroethyl-2-methyl-4-aminobenzaldehydeare added and the mixture is heated to the reflux temperature forseveral hours, until the β-chloroethyl-aldehyde is virtually no longerdetectable by chromatography. After cooling, thepentachlorophenylmercapto-aldehyde can be isolated in good yield in theabovementioned manner.

The same result is obtained if the procedure of Example 1 of GermanOffenlegungsschrift (German Published Specification) No. 2,301,461 isapplied to pentachlorothiophenol.

If the aldehyde of the preceding example is reacted analogously withcyanoacetic acid derivatives instead of with malodinitrile, dyestuffswith comparably valuable tinctorial properties are again obtained. Someexamples are summarised in the table which follows. The shades of theirdyeings on polyester fibres and cellulose triacetate fibres arethroughout somewhat more greenish-tinged than the colour shade of thecorresponding malodinitrile dyestuff.

    ______________________________________                                         ##STR17##                                                                    Ex-                                                                           am-                                                                           ple                                                                           No.  Z               Colour shade on polyester fibres                         ______________________________________                                         2   COOCH.sub.3     Strongly greenish-tinged yellow                          3    COOC.sub.2 H.sub.5                                                                            "                                                        4    COOC.sub.2 H.sub.4 OCH.sub.3                                                                  "                                                        5    COOC.sub.3 H.sub.6 OCH.sub.3                                                                  "                                                        6    COOC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                           "                                                        7    COOC.sub.3 H.sub.7 (n)                                                                        "                                                        8    COOC.sub.2 H.sub.4 CN                                                                         "                                                        9    COOC.sub.4 H.sub.9 (n)                                                                        "                                                        10   COOCH.sub.2C.sub.6 H.sub.5                                                                    "                                                        11   COOC.sub.2 H.sub.4C.sub.6 H.sub.5                                                             "                                                        12   COOC.sub.3 H.sub.6C.sub.6 H.sub.5 (n)                                                         "                                                        ______________________________________                                    

The table which follows describes, in further examples, dyestuffsaccording to the invention which are obtained analogously to Example 1by condensation of analogously prepared aldehydes with malodinitrile orcyanoacetic acid derivatives, and also the colour shade of theparticular styryl dyestuff on polyester fibres and cellulose triacetatefibres.

    __________________________________________________________________________    Example                                                                            Structure                     Colour shade                               __________________________________________________________________________    13                                                                                  ##STR18##                    Greenish-tinged yellow                     14                                                                                  ##STR19##                    "                                          15                                                                                  ##STR20##                    "                                          16                                                                                  ##STR21##                    "                                          17                                                                                  ##STR22##                    "                                          18                                                                                  ##STR23##                    "                                          19                                                                                  ##STR24##                    "                                          20                                                                                  ##STR25##                    "                                          21                                                                                  ##STR26##                    "                                          22                                                                                  ##STR27##                    "                                          23                                                                                  ##STR28##                    "                                          24                                                                                  ##STR29##                    "                                          25                                                                                  ##STR30##                    Slightly greenish-tinged yellow            26                                                                                  ##STR31##                    "                                          27                                                                                  ##STR32##                    "                                          28                                                                                  ##STR33##                    Greenish-tinged yellow                     29                                                                                  ##STR34##                    "                                          30                                                                                  ##STR35##                    "                                          31                                                                                  ##STR36##                    "                                          32                                                                                  ##STR37##                    "                                          33                                                                                  ##STR38##                    "                                          34                                                                                  ##STR39##                    "                                          __________________________________________________________________________     * The radical Cl.sub.5 C.sub.6 represents a pentachlorophenyl radical    

EXAMPLE 35

1 part of a dyestuff of the formula ##STR40## is dissolved in 25 partsof dimethylformamide, 1 part of a dispersing agent (alkylaryl polyglycolether) is added and a fine dispersion is prepared by stirring themixture into 4,000 parts by volume of water. In addition, 20 g of acarrier (cresontic acid ester) and 4 g of monosodium dihydrogenphosphate are added and the pH value of the dye bath is adjusted to4.5-5 with acetic acid. 100 parts of previously cleaned polyestermaterial (polyethylene glycol terephthalate fibres of the Dacron type,of Messrs. Dupont are introduced into the dyebath at 40°-50° C., thetemperature is raised to 80°-85° C. over the course of 15-20 minutes andis kept thereat for 20 minutes, and the bath is now gradually brought tothe boil. After boiling for 1-1.5 hours, the dyeing process is complete.The dyed material is rinsed once hot, and is then rinsed cold and dried.It exhibits a clear, greenish-tinged yellow coloration of very goodfastness to light, washing and sublimation.

The dyestuff can also be used as a compounded paste or compounded powderby grinding it, as an aqueous paste, with dispersing agents (for exampleligninsulphonates) and, if appropriate, subsequently drying it.

If the conjoint use of a swelling agent (carrier) is dispensed with, acomparable dyeing is obtained on using a liquor ratio of 1:20 andemploying the known high temperature dyeing process (HT process). Hereagain the prepurified polyester material is introduced at 40°-50° C.into the otherwise similarly prepared dyebath, the bath temperature israised to 125° C. for 30-40 minutes and the material is dyed for 1-1.5hours at 125°-130° C.

EXAMPLE 36

100 parts of a fabric of cellulose triacetate rayon is dyed for 1 hourat the boil in a dyebath prepared from 1.5 parts of the dyestuffaccording to Example 13, 4 parts of Marseilles soap and 4,000 parts byvolume of water. The resulting greenish-tinged yellow dye has very goodfastness properties.

EXAMPLE 37

1,000 parts of polystyrene are mixed with 6 parts of the dyestuffaccording to Example 27 and the mixture is fused in the usual mannerunder a nitrogen atmosphere at about 200° C. The greenish-tinged yellowinjection mouldings obtained from this material show good fastness ofthe colour.

I claim:
 1. Water-insoluble styryl dyestuff of the formula ##STR41##wherein B is C₂ -C₅ -alkylene; C₂ -C₅ -alkylene interrupted by an oxygenatom or sulphur; or the foregoing substituted by C₁ - to C₄ -alkoxy, C₁-C₄ -alkenyloxy, benzyloxy or phenoxy;n is 3 to 5;wherein the ring "b"is further unsubstituted or substituted by C₁ - to C₄ -alkyl, C₁ - to C₄-alkoxy, --CN or --COOH; Y₁ is hydrogen, C₁ - to C₄ -alkyl, C₁ - to C₄-alkoxy, CF₃, C₂ - to C₄ -alkanoylamino, phenoxy, F, Cl or Br; and R andY₂ conjointly form the missing members of an unsubstituted1,2,3,4-tetrahydroquinoline ring or a 1,2,3,4-tetrahydroquinoline ringmono-, di- or tri-substituted with methyl or ethyl or mono-substitutedwith chlorine.
 2. Water-insoluble styryl dyestuff of the formula##STR42## wherein X is C₁ - to C₄ -alkyl, C₁ - to C₄ -alkoxy, CN orhydrogen;n is 4-5; B' is --C₂ H₄ --, --C₃ H₆ --, --C₄ H₈ --,--CH(CH₃)CH₂ --, --CH(C₆ H₅)CH₂ --, --CH(CH₂ OCH₃)CH₂ --, --CH(CH₂ OC₂H₅)CH₂ --, --CH(CH₂ OCH₂ CH═CH₂)CH₂ --, --CH(CH₂ OC₆ H₅)CH₂ -- or--CH(CH₂ OCH₂ C₆ H₅)CH₂ --; Y is hydrogen, C₁ - to C₄ -alkyl, C₁ - to C₄-alkoxy, CF₃, C₂ - to C₄ -alkanoylamino, phenoxy, F, Cl or Br; R' and Y₂conjointly form the missing members of an unsubstituted1,2,3,4-tetrahydroquinoline ring or a 1,2,3,4-tetrahydroquinoline ringmono-, di- or tri-substituted with methyl or ethyl, or mono-substitutedwith chloro.
 3. Water-insoluble styryl dyestuff of claim 2 whereinY₁ ishydrogen or methyl; and B' is ethylene.
 4. Styryl dyestuff according toclaim 2, of the formula ##STR43##